Polyvinyl acetate emulsion containing an alkyl amide, and base coated therewith



Patented May 6, 19152 UNITED STATES POLYVINYL ACETATE EMULSION CONTAIN- ING AN ALKYL AMIDE, AND BASE COATED THEREWITH rarest @FFICE setts No-llrawing. Application April 6, 1950, Serial No. 154,426

8 Claims.

This invention relates to emulsions of polymers which are suitable for use as coatings and as adhesives. It is particularly concerned with such an emulsion of polymers which is capable of providing a water-resistant bond or coating and which at the same time retains the stability, fluidity and'the various other physical properties of such an emulsion which make it particularly useful as a coating or adhesive.

The use of melts and solutions of water-insoluble artificial resins in the coating and adhesive art has-been supplanted to a large extent by emulsions of such resins, particularly polyvinyl acetate emulsions, due to the improved ease, economy and safety with which aqueous emulsions of the resin may be' employed. On the other hand, the usefulness of water insolublc polymer emulsions has been limited by the characteristic lack of water-resistance of the coatings and bonds deposited therefrom at room temperature and. the tendency-of such coatings and bonds to re-emulsifyor disintegrate when subsequently brought into contact with water during the course of normal use of the object or article to which they have been applied.

This lack of water-resistance has been considered innate in the coatings and films deposited from suchpolymer emulsions inasmuch a'swatersoluble emulsifying and bodying agents are employed necessarily to establish and stabilize the emulsion. These agents are apparently carried into the film orbond deposited from the emulsion upon application of the emulsion to a surface, and actively exhibit the emulsifying effect on the polymer comprising the body of the coating or film and cause its redispersion when the surface is brought into contact with water.

Various proposals have been made to obviate the water-sensitivity of the coating or bond deposited from such emulsions, but in general these proposals have been directed to modifying emulsions' of such polymers which have been prepared in a specific manner, or require treating the emulsion with certain diluents immediately prior to its application due to the recognized tendency of the suggested diluents to either break or gel the emulsion shortly after the addition of the diluent.

Prior to the instant invention, forexample, a common expedient for increasing the waterresistance of a coating or film deposited from a water-insoluble polymer emulsion included the addition of a quantity of one or more substances such as dimethylol urea, trimethylol melamine, certain chromium salts, strong acids or highly reactive aldehydes such as glyoxal, certainresins, toluene and peroxides. In most instances it was required that the substances be added to the polymer emulsion immediately prior to'useas the resulting compositions were'unstable and certain of the substances resulted in a progressive increase in the viscosity of the emulsion until a gel was formed. Gelling rendered the composition unfit for use in adhesive applicator machines operated at high speed. Additionally, the modification effected by some of these substances did not result in a substantial improvement in the water-resistance of the coating or film deposited from the emulsion, and often imparted undesirable color and foaming characteristics to the emulsion.

Where thermo-plastic polymeric material has been employed it has been suggested that the water-resistance of the coating or bond deposited from an emulsion of the material can be improved by heating the coating-orbond sufiiciently to cause coalescence of the material into a homogeneous mass. This procedure is obvious- 1y not suitable where the'emulsion is employed as aquick-setting adhesive in high-speed mechanical applicators, and in any event, the drying and heating suggested is often impractical.

A further suggestion directed-to retaining the advantages of working with the polymers in an aqueous medium and at the same time avoiding the inherent disadvantages of water-sensitivity of the coatings or films deposited therefrom required dispersing the polymer as extremely-small particles. The coatings or films deposited from such emulsions do exhibit a satisfactory waterresistance but due to the fine particle size which imparts the water-resistance, the "emulsions'do not have the tack necessary to make them useful as quick-setting adhesives.

It is an object of this invention to provide a composition comprising an aqueous emulsion of a polymer, particularly a polymer of vinyl acetate, alone or in combination with small quantities of other monomers, which is stable throughout long periods of storage, and whichwhen employedas a coating or as an adhesive will deposit a coating or bond which is highly water-resistant. A further object of the invention is to providea process which is generally applicable to modify emulsions of polymers, particularly polyvinyl acetate, which have been polymerized to different extents, or'in different manners, and which include various combinations of plasticizers and other diluents commonly employed to develop favored characteristics in the films or coatings deposited from such emulsions.

We have discovered that the water-resistance of coatings or bonds deposited from an aqueous emulsion of polymers, particularly polyvinyl acetate emulsions, which are formulated, or modilied, to have a tackiness rendering them suitable for use as quick-setting adhesives, can be established by additions of one or more of a certain group of organic compounds within specific limits. These active compounds are characterized by a particular balance between the parts of the monomeric molecule, one part of which is hydrophilic or polar in nature, and the other part of which is hydrophobic or non-polar. The effectiveness of the compounds in producing water-resistance in the coatings or bonds deposited from such emulsions is apparently due to the presence of both the polar and non-polar groups within the molecule in the prescribed balance. As a class, these active compounds exhibit solubility, to various extents, in both water and in organic solvents such as mineral spirits, petroleum ether, toluene, castor oil, etc. This solubility in both Water and organic solvents apparently is due to the dual hydrophilic-hydrophobic nature of the compound. As it has been generally recognized that the presence of water-soluble emulsifiers carried into the bonds and coatings deposited from emulsions of waer-insoluble polymers may later cause redispersion and disintegration of the bonds and coatings, it was particularly surprising to find that incorporating into th emulsion additional compounds which are water-soluble themselves will nullify the efiect of the water-solubl emulsifiers and thereby impart water-resistance to the coatings and films deposited from such emulsions.

For present purposes a polar or hydrophilic group or radical may be considered to be one which has a strong amnity for water and which when combined in compounds in which it is the dominant functional group will cause the resulting compound to be immiscible, or miscible to a limited extent, in oil-type solvents. A non-polar or hydrophobic group, on the other hand, may be considered to be one which has slight aflinity for water and a strong aflinity for oil-type solvents. In general, the amide group displays the characteristics of a suitable polar group.

The open chain type carbon compound groups are typical non-polar groups. Accordingly, within certain limits the aliphatic type amides are effective in imparting water-resistanc to th films or coatings deposited from polyvinyl acetate emulsion.

We have found that the alkyl amides having a total of from 4 to 6 carbon atoms are particularly suited for this purpose. These amide are soluble in water to an extent which permits an effective quantity of the compounds to be readily incorporated into the starting material emulsion.

The requisite polar-non-polar balance within the molecule first appears in propionamide. In

this instance the amide group i effectively balwhen propionamide is employed in equal quantities. Formamide and acetamide are not active. The polar portion of these molecules apparently dominates the molecule and the prescribed polarnon-polar balance is not obtained. Caprylamide, and heptylamide are somewhat too hydrophobic in character and due to their limited solubility cannot readily be taken into solution in quantities required to produce the desired water-resistance.

The preferred range of total quantities of one or more of the active compounds by weight with respect to the solid content of the polyvinyl acetate emulsion has been found to be between about 4-25%, the optimum amount in a particular instance depending upon the initial water-resistance characteristics of the starting material emulsion, the amount of plasticizers employed,

.and the age of the starting material emulsion.

The physical properties of a polyvinyl acetate emulsion such as the viscosity of the emulsion, and the tensile strength, flexibility and heat sealing temperature of the film or bond deposited from the emulsion are determined in a large part by the degree of polymerization of the vinyl acetate monomer. A higher degree of polymerization results in increased bond strength, a higher heat sealing temperature and a somewhat higher initial water-resistance, which is, however, considerably less than required commercially for a water-resistant coating or bond. A lesser quantity of the active compounds is necessary to impart the desired water-resistance to the deposited coatings or bonds when the relatively greater water-resistant emulsions are employed as a starting material.

The polyvinyl acetate starting material emulsions having sufficient tack to be useful as quicksetting adhesives generally contain about 40-65% polyvinyl acetate by weight. Such emulsions include the commercially available polyvinyl acetate emulsions known as Elvacet -900, Elvacet 81-900, Gelva 8-50, Polyco ll'l-H, Polyco ll'l-SS and Polyco 289. However, a dried bond produced by these emulsions between two sheets of mildly calendered white sulphite paper will disintegrate within 24 hours of immersion in water at about 25 C.

The physical characteristics of the commercially available polyvinyl acetate emulsions identified above may also vary to some extent as a result of the emulsifiers and bodying agents employed in producing the emulsions, and also as a result of particular plasticizers employed. Here again, however, the variations which tend to increase the relative initial water-resistance of the starting material and emulsions lessen the quantity of the active compounds required to efiect complete water-resistance.

The amounts of active compound required to produce maximum water-resistance in a particular emulsion also varies with the quantity and the nature of the plasticizers, extenders, or other diluents which may be used to develop desired characteristics of fluidity or tackiness in the emulsion, or of flexibility, hardness, etc. in the coating or film deposited from the emulsion. In general, it has been found that the insoluble type of plasticizers and resins in common use increase the efiectiveness of the active compounds, and that a lesser quantity of active compound is necessary to produce complete waterreslstance when such plasticizers are also present in the emulsion. It should be noted, however, that in each instance the emulsion containing the plasticizers and various other diluents was not initially wa'ter-resistantand that the additionof the active compound was-necessary to effect any satisfactory water-resistance although as related above, a lesser amount is necessary when insoluble plasticizers are also present.

This enhancing effect of the insoluble plasticizers was particularly observed with respect to dimethyl phthalate, dibutyl phthalate, chlorinated diphenyls, methyl abiatate and tributyl phosphate, and appears to be characteristic of other common plasticizers such as di-carbitol phthalate, dibutoxy-glycol phthalate, dimethoxyglycol phthalate, butyl phthalyl butyl glycolate, methyl phthalyl ethyl glycolate, triglycol (ii-2- ethylbutyrate, triglycol di-2-ethylhexoate, tricresyl phosphate and triphenyl phosphate.

On the other hand, the presence of a small amount of certain water-soluble thickeners such as polyvinyl alcohol and sodium carboxymethyl cellulose tend to'increase theamount of active compound. necessary to efiect maximum waterresistance.

In some instances care must be exercised. to avoid breaking the emulsion by sudden heating, or by extended heating above the temperature specified. The critical temperature will vary, of course, with the character of the particular starting material emulsion employed.

Aging the composition also tends to increase the water-resistance of the coatings or films deposited therefrom.

It will be apparent from the foregoing that innumerable possibilities for formulating the instant water-resistance composition exist, and

that the invention may be practiced to increase the water-resistance of any particular polyvinyl acetate emulsion without materially interfering with the versatility of the starting material emulsion. It will be noted, however, that any of the active compounds having the requisite polarnon-polar balances in the molecules thereof are effective in producing water-resistance when used in quantities within the range of 425% by weight of the solids present in the starting material polyvinyl acetate emulsion. The minimum amount of a particular one of the active compounds depends upon the factors discussed above, but in all instances is within the specified range.

Compositions having up to 50% by weight of active compound with respect to the solid content of the polyvinyl acetate starting material emulsion may be employed, especially if high fluidity is desired in the finished composition and the active compound has desirable plasticizing properties.

It will be understood that the composition of the films and bonds deposited from the type of emulsion dealt with here is the same as the emulsion except for the external water phase which evaporates upon drying.

The addition of the active compound to the starting material emulsion may result in a substantial increase in the viscosity of the emulsion to form a cohesive mass unless the active compound is added slowly with continuous agitation. In some instances rapid addition of the active compound results in localized precipitation of the emulsion. The largest part of the increased cohesiveness and viscosity of the emulsion caused by addition of the active compound at a suitable rate disappears on agitation, or when the treated emulsion is permitted to stand for a short period following the addition of the active compound.

In all of the following examples the compositlon was prepared by stirring the starting materia'l emulsion with a high-speed mixer continu ously during the addition of theactive compound' thereto; The active compound was introduced into'the emulsion at the rate of about 3% of thetotal weight of the active compound per minute.

Each of the tacky starting'material polyvinyl emulsions'was applied as :a coating on thesurface of a'moderately calendered and" sized white sulphite' paper and as a bond .between two'such papers. The filmsandbondsthus formed'were allowed to dry for 24 hours at .ro'omtemperatureand were thereafter immersed in water'at room' temperature for 24 hours. Upon removal .from the water-the wet strength ofthe paper exceeded the bond strength in all cases, and the bond ruptured. when thebonded papers. were separated.v

The: coatings in each'instance had visibly disinteg-rated.

of the bond exceeded the wet strength of the paper after 24 hours immersion. I

Example 1 A first sample was prepared by mixing parts of a tacky polyvinyl acetate emulsion having about 55% solid content with 6 parts of a dimethyl phthalate plasticizer. The emulsion was stirred continuously with a high-speed mixer during the addition of the plasticizer thereto.

Five additional samples were prepared by. first preparing a 50% water solution of butyramide. Thereafter, 5 mixtures comprising 110 parts of a tacky polyvinyl acetate emulsion having about 55% solid content and 6 parts of a dimethyl phthalate plasticizer were made up. The starting material emulsion was stirred continuously with a high-speed mixer during the addition of the plasticizer thereto. Thereafter, the butyramide solution was added to each of the five mixtures in amounts to introduce, respectively, 8, 10, 12, 15 and 20% butyramide by weight of solid content of the starting material emulsion into the sample. The butyramide solution in each instance was added slowly while the mixture was stirred continuously with a high-speed mixer.

All the samples were tested for water-resistance by applying them as both a film and bond to a mildly sized and calendered white sulphite paper. The films and bonds were allowed to dry for 24 hours and were thereafter immersed in water at room temperature for an additional 24 hours. The films and bonds deposited from the sample consisting of starting material emulsion and plasticizer were not water-resistant. At the end of the period of immersion the film had visibly disintegrated and could be easily rubbed off the paper. The wet strength of the paper exceeded the bond strength so that the bond fractured when the bonded papers were separated. The samples containing the butyramide were waterresistant. At the end of the immersion period the films were continuous and intact. The bond strength exceeded the wet strength of the paper so that the surfaces of the paper were torn when the bonded papers were separated.

Example 2 These starting. material emulsions were, therefore, considered non-water-resistant,

ate and propionamide was employed in place of the butyramide used in Example 1.

These samples were tested for waterproofness in the manner described in Example 1. It was again found that the films and bonds deposited from the composition consisting of starting material emulsion and plasticizer were not waterresistant. The films had partially redispersed and disintegrated during the period of immersion. The wet strength of the paper again exceeded the bond strength so that the bond was fractured when the bonded papers were separated. The films and bonds deposited from the sample containing propionamide were water-resistant. At the end of the period of immersion the films were continuous and intact. The bond strength exceeded the wet strength of the paper, so that the paper was torn, the bond remaining intact, when the bonded papers were separated.

It will be apparent that the water-resistant compositions formulated according to the instant invention will considerably extend the usefulness of the aqueous emulsions of polyvinyl acetate into the field in which high water-resistance of the bond or coating deposited is necessary and will find application in bonding or cementing for cellulosic articles such as paper cups or paper bags which in the course of normal use are exposed to water and for bonding surfaces of cellulosic material to other surfaces of a hydrophilic character such as masonry. These compositions are particularly adapted for use as a sizing where water-resistance of the fabric or the paper to which it is applied is required. It may also be employed in the composition of printing paste, as a finish for paper, paper-board, or foils and in the manufacture of formed or impregnated goods, as well as distemper paints and the like.

Having thus described the invention, what is new and desired to be secured by Letters Patent is: 4

1. A composition comprising a tacky aqueous emulsion of polyvinyl acetate and 450% by weight of said acetate of an organic compound consisting of an amide group and an alkyl group having 3 to 5 carbon atoms.

2. A composition comprising a tacky aqueous emulsion of polyvinyl acetate and from 4 to by weight of said acetate of an alkyl amide having 4 to 6 carbon atoms.

3. A composition comprising a tacky aqueous emulsion of polyvinyl acetate, a plasticizer for said acetate and from 4 to 50% by weight of said acetate of an alkyl amide having 4 to 6 carbon atoms.

4. A composition comprising a tacky aqueous emulsion of polyvinyl acetate, and from 4 to 50% by weight of said acetate of a water-soluble alkyl amide having 4 to 6 carbon atoms.

5. A composition comprising a tacky aqueous emulsion of polyvinyl acetate, and from 4 to 50% by weight of said acetate of butyramide.

6. A composition comprising a tacky aqueous emulsion of polyvinyl acetate, and from 4 to 50% by weight of said acetate of proprionamide.

'7. A composition comprising a tacky aqueous emulsion of polyvinyl acetate, and from 4 to 50% by weight of said acetate of valeramide.

8. A base having a water resistant coating deposited thereon from a composition comprising a tacky aqueous emulsion of polyvinyl acetate and an alkyl amide containing 3 to 6 carbon atoms.

WALTER G. KUNZE. R. BERTRAM EVANS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,070,991 Hund et al. Feb. 16, 1937 2,444,396 Collins et al. June 29, 1948 

1. A COMPOSITION COMPRISING A TACKY AQUEOUS EMULSION OF POLYVINYL ACETATE AND 4-50% BY WEIGHT OF SAID ACETATE OF AN ORGANIC COMPOUND CONSISTING OF AN AMIDE GROUP AND AN ALKYL GROUP HAVING 3 TO 5 CARBON ATOMS. 